Cyclooctanone → Cyclooctanol, 1-ethynyl-

HRID 1363952Notes

Reaction equation

HRID 1363952 reaction equation
[C-]#[C-].[Li+].[Li+].[CH2:5](N)[CH2:6]N.[C:9]1(=[O:17])[CH2:16][CH2:15][CH2:14][CH2:13][CH2:12][CH2:11][CH2:10]1.[NH4+].[Cl-]>C1COCC1>[C:5]([C:9]1([OH:17])[CH2:16][CH2:15][CH2:14][CH2:13][CH2:12][CH2:11][CH2:10]1)#[CH:6]

Participants

5

Reactant 3

HCID 10403CyclooctanoneHCID 25517Ammonium ChlorideHCID 178511344HCID 178511344, compound

Product 1

HCID 123539Cyclooctanol, 1-ethynyl-Yield 106.7%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
45 °C

Procedure

At 35° C., a solution of lithium acetylide-ethylene diamine (50 g, 0.49 mol) in THF (500 ml) was slowly treated (reaction temperature ≦35° C.) with a solution of cyclooctanone (51.4 g, 0.41 mol) in THF (100 ml). The resulting mixture was stirred for 4 h at 20° C., 15 h at 45° C., cooled to 5° C., treated with aqueous sat. NH4Cl solution (250 ml) and washed with 3M aqueous HCl. After extraction with Et2O, the organic phases were washed with water, aqueous sat. Na2CO3 solution, dried (Na2SO4), and concentrated to give 1-ethynylcyclooctanol (66.6 g). A solution of crude 1-ethynylcyclooctanol (65 g) in formic acid (130 ml) was heated for 2.5 h at 80° C. The resulting mixture was taken up in Et2O and washed successively with water, 5M NaOH, water, aqueous sat. NH4Cl solution, dried (Na2SO4), and concentrated to give 56 g of crude product. A fraction (8 g) was purified by flash chromatography (hexane/Et2O 95:5→9:1) to give 4.1 g of 1-cyclooct-2-enylethanone.

Workup

  1. temperaturecooled to 5° C.
  2. washwashed with 3M aqueous HCl
  3. extractionAfter extraction with Et2O
  4. washthe organic phases were washed with water, aqueous sat. Na2CO3 solution
  5. dry with materialdried (Na2SO4)
  6. concentrationconcentrated

Sources & evidence

ORD record
ord-07762aaee862452ab49b806b5a4bb66f
Source dataset
uspto-grants-2011_02
Patent number
US07888309B2

Reaction notes

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